Process of forming spheroidal catalyst particles



P 15, 1953 J. GRING 2,652,371

PROCESS OF FORMING SPHEROIDAL CATALYST PARTICLES Filed Dec. 20, 1949 oaLmus ANGLE J LAYER RECYCLE SOLUTION 10 30 11' I? 15% J INVENTOR. JOHN L. GRIMG 2%, FM M- ATTORNEYS.

liquid.

Patented Sept. 15, 1953 PROCESS OF 'FORNHNG, SPHEROIDAL.

CATALYST PARTICLES John'LfGring, Homewood, 111., assignor to Sin- (flair-Refining Company, New York, NJ-YL; a

corporation' otMaine Application December 20, .1949, Serial No. 134,075

Z-GIai m s. 1. My invention. relates tojthe,.preparation and size classification fof small substantially spherical, solid particles formed from..a,coagu1ative Various. proposals have been. made, to .prepare small, solid particles such. as. microspheres.

. for many uses of these solid microspheres, e; g.,

when they are employedascatalysts or catalyst components in variouscatalytic. operations. In particular, homogeneous. silica gel. microspheres, because of their spherical ,formwand size similarity, provide excellent catalyst. components for fluid catalyst cracking.

I have now discovered. that. small,{substantially spherical, solidparticlescan be. formed and accurately size classified org'raded in asurprisingly simple, single. operation. which .comprises discharging as a streamofdroplets'. -a .coagulative liquid at an obliqueangle, segregating the discharged droplets according tothe difference in their trajectories orpaths and selectively collecting homogeneous solid particles of. desired size range. The discharge droplets are. solidified by any suitable means after discharge and before collection. In addition, I have found it useful to subject the discharge streambcfore segregation to a cross-flow gas stream which will further improve the size classification. The. oblique angle can be supplied by simply discharging the liquid at any angle between the horizontal-sandvertical from a conventional nozzle capable of-delivering the liquid as a stream of droplets. Or theliquid may be discharged from avertically-placed spray line to which is aflixed a nozzleicapable of projecting the dischargestream outwardly sothat it then falls atthe oblique angler Or, the spray stream can be directed downwardly and the oblique angle of thestream trajectory-or path supplied by at least one side cross-flow gas stream which will divert it from a normal gravity fall, the particles being selectively collectedat intermediate points in the path of the streamand/or at the end of the .path. The.discharge-liquid may comprise solutions or slurries capable of being ooagulated or hardened, for. instance, a stable aqueous sodium silicate solution, a hydrogel slurry or a hydrosol. The droplets may be solidifiedor hardened in avarietyofways sayvby gelling in an acidic mediumwhich ma be agas or a liquid, by simple hardening or coagulation in air with orwithout the aid or heat.

The size classification process according to-my invention is predicated in large measure upon the physical phenomenon that the trajectories of the individual droplets will vary depending upon their size. Due to the interaction and/or the effect of gravity, the massvelocity force and atmospheric friction, the. droplets of small size, for instance, will commence gravitating nearer to the spray orifice, than will the larger droplets. That is, the trajectories of thedroplets of small size will be less than those of'droplets oi greater size. In addition, since the droplets emerging from an atomized spray stream will; vary ininitial velocity, it is, advantageous to subjectg the discharge stream oi spray droplets to a crossflow gas stream to improve size classification. In this way, particles ofghighvelocity-low mass; and

. low velocity-high mass will have similar trajectories and the cross-flow stream will substantially divert the smaller. particles in-spite of their greater velocity.

To brieflyillustrate one specifiqembodiment of .my. invention, an aqueous sodium silicate solu- J tion is atomized. at an obliqueangle into air, the

discharged droplets, being, segregated according to. the difierence in their trajectories and the droplets of desiredsizerangepassinginto a gelli vironme t rzon whe n they ar h r n a d h co lect d; The disc ar Stream is ass d a th en o ts, tra ct y th ou h a s s s t nam cn .Qqmrri i sf a p urali of vertically inclined troughs with, anger more slitlike openings. Dropletsofi desired size of sodium silicate solution pass between the-slit-like openings into a gelling zone, advantageously containing an acidicagent, while droplets of undesired size are collected in the vertically inclined troughs and recycled for subsequent discharge. Advantageously, a. cross-flow gas stream, say of air, is projected ,across the, sodium silicate stream at an intermediate point betweenthe" discharge means and segregation barriers. ,Ihis cross-flow stream alters .the trajectory of the drcplets in the main discharge ,streamby modifying the path of, for instance the smaller e press and thereby improving the, size classification. jIhus the droplets of high velocityrlow mass will be prevented from assuming a trajectory identical with those of low velocity-highmass'whichmay disturb the accuracy. Qf thesize classification.

In anotherspecific embgdiment or my invention, a stream of droplets, of a,coagulativeliguid 1 ets or collection troughs, are projectedacioss the gravitating stream which divert some of the droplets into these pockets. Additional particles collect at the bottom of the tower or a gelling environment may be provided there for forming solid microspheres of those particles of the desired size range.

Still another specific embodiment of my invention comprises discharging the coagulative liquid from a spray line vertically located and to which is afiixed a suitable nozzle which projects the discharge stream outwardly at the oblique angle. For instance, a disc type nozzle or a sprayer containing a plurality of openings obliquely located in an inverted comb will provide the oblique angle of discharge. The discharge stream then passes through a segregation means which permits only those droplets of desired size to enter a drying or gelling chamber. This method is ideally suited for discharging a hydrogel slurry, the droplets of desired size being segregated and are then allowed to pass into a drying chamber directly beneath the segregation means. The hardened or dried particles of desired size are then collected at the bottom of the chamber. I

The coagulative liquid is discharged as droplets and where minute particles are required this is advantageously accomplished by the use of an atomizer. In any event the discharge mechanism will comprise any sprayer that will deliver the liquid as a stream of droplets at the required angle. As I have already indicated, the oblique angle of discharge may be supplied in a variety of ways, for instance, by discharging the liquid at any angle between the horizontal and vertical from a sprayer so positioned. Or the sprayer may be so constructed as to deliver the discharge stream at the oblique angle although the nozzle itself is vertically located. On the other hand, the spray stream can be initially delivered vertically and the oblique angle or stream trajectory supplied by at least one side cross-fiow gas stream- The segregation means will be adapted to the droplet stream that is to be size classified. Advantageously, I contemplate a segregation means comprising a plurality of properly-positioned barriers or troughs with suitably placed openings between them. In this way, the droplets of desired size pass through the openings, while the droplets of undesirable size are collected in the troughs where they may be collected for redischarge. In this regard, when the liquid is atomized into a stream of droplets, such as of aqueous sodium silicate, and then passed into a gelling environment or zone, the segregation means preferably comprises vertically inclined troughs with slit-like openings between them. Droplets of desired size thus pass into a gelling or hardening zone directly beneath the troughs by means of the small openings between them, while the remaining droplets are collected and recycled for subsequent discharge. of course, the barriers or troughs are so positioned with respect to the openings between them to take into account the varying trajectories of the particles to be segregated. Where the discharged liquid does not gel or harden too rapidly as in the case of using an aqueous sodium silicate solution for discharge, it is simple to recycle the solution of the rejected droplet for redischarge. When the droplets are gravitated vertically downwardly in a stream, the collection troughs or barriers are located at the sides of an elongated tower, gas side streams along the vertical path blowing or diverting some of the droplets into them, while additional droplets may be also collected at the bottom of the tower.

The droplets may be solidified or hardened at any point intermediate to discharge and ultimate collection, although in the examples I have mentioned the hardening or solidifying is accomplishedsubsequent to segregation. The solidification may be accomplished in a variety of ways depending in large measure upon the discharge material. For instance, where an aqueous sodium silicate solution is employed, the droplets of desired size are advantageously gelled in an acidic medium, usually in liquid phase. However, the gelling material may comprise a fine acid mist or other suitable hardening means.

Where a hydrogel slurry, say silica hydrogel, is

discharged, the droplets are hardened simply by passing them through air which may be heated to elevated temperatures to accelerate hardening.

The discharge material in general includes coagulative liquids of the nature of sodium silicate solutions, hydrogel slurries or hydrosols. A stable aqueous solution of sodium silicate is particularly advantageous since it is readily susceptible of gellation while at the same time the solution collected at the segregation troughs may be easily recycled. On the other hand, a dispersed hydrogel slurry is useful for discharge. I particularly include hydrogel slurries containing in the nature of about 10 by weight of solids in an aqueous material. Here again the rejected droplets may be collected for redischarge, although they may have to be worked up again. Hydrosols may be used for discharge in accordance with my invention. Although silica hydrosol, for instance, may gel before collection and recycling, thefines-forming droplets and the coarser than mesh-forming droplets can still be removed from the stream. The discharge material may even include multi-component systems, such as slurries of magnesia-silica hydrogel, or of silica alumina hydrogels or of silicamagnesia-alumina hydrogels, and so forth.

Droplets forming particles in a wide range of the smaller sizes may be classified according to my process and my invention is not limited to any specific range. For instance, using a stable aqueous solution of sodium silicate, particles which will ultimately yield components ideally suited for fluid catalyst cracking, i, e., those in the size range corresponding to to 200 mesh, are classified.

A preferred embodiment of my invention comprises using a spray stream of aqueous sodium silicate solution. In my copending application Serial No. 54,817, filed October 15, 1948, I have already described a method whereby a stable aqueous solution of sodium silicate can be sprayed or atomized into an acidic gelling environment so as to produce firm, substantially spherical particles of silica gel. The resulting microspheres may be processed by Washing impregnation, precipitation, and the like, to yield effective catalytic compositions. The acidic zone, most advantageously, comprises an upper layer of an acidic agent, say sulfur dioxide in oil, and a lower layer of a dilute acid, say dilute sulfuric acid. Thus the particles of silica gel settle from the acid oil and collect in the dilute aqueous acid layer from which they may be continuously withdrawn.

The size of the silica gel spheres is essentially determined by the dispersion step. For instance, el spheres which Will produce a final microspherical product in the approximate range of from to 100 microns are produced by spraying the solution through an orifice of 0.018 inch in diameter. With gas or vapor atomization of the silicate solution, the particle size is also largely controlled by variation in the spray pressure. Other factors of consequence are variations in the density andv temperature of the silicate solution, the velocity with which the silicate solution. hits the oil surface, and the viscosity of the oil.

spheroidal particles thus prepared may be employed as catalyst components for a variety of different cracking catalysts. Generally, catalyst components formed in this manner are utilized in hydrocarbon conversion processes directed towards amination, polymerization, hydrogenation, dehydrogenation, alkylation, Fischer- Tropsch conversion, and the like. Specifically, these catalysts are particularly valuable in those pyrolytic conversions of hydrocarbons involving the use of catalysts wherein a finely divided solid contact material is transported in a fluid stream through various zones of treatment, a conversion method commonly identified as fluid catalytic cracking.

Figure 1 is a cross-sectional side view showing somewhat schematically the process of my invention wherein a stable aqueous sodium silicate solution is dispersed as the stream, illustrating particularly the atoinizing or discharge means, collection troughs and the acidic gelling zone.

Figure 2 is a top view of the apparatus illustrated in Figure 1, showing especially the recycle provisions in the flow diagram,

As illustrated in Figures 1 and 2 of the accompanying drawings a solution of stable aqueous sodium silicate is passed through line it to atomizing nozzle H by pump it. The stream is projected into an inert gaseous atmosphere it, advantageously air, at an oblique angle E2, in a trajectory leading to an acidic gelling zone Hi. The acidic gelling zone I l comprises an upper layer It of sulfur dioxide dissolved in oil and a lower layer it of dilute acid, say dilute sulfuric acid. Vertically inclined collection troughs or barriers Il', ill and i9 prevent droplets of undo-- sired size from passing into the acidic gelling environment M- and. wherein the silicate solution is collected for recycling. The recycle solution flows from the vertically inclined troughs into lines 29, 2! and 22, then to line 2% for redischarge by line it: pump Fresh sodium silicate solution is introduced through line 3?. The stream as schematically illustrated may comprise trajectories 3t, 32, 33 and. 3 for the various sized particles. The trajectory 32 of the droplets to be collected passes through an opening between barrier H and I8 into acidic zone It. Pump 25 removes the gaseous sulfur dioxide by vent line 26 that may rise out of the acid layer I5. The gelled silica microspheres pass through the acid layers and are collected at the bottom 2'! of the lower zone I6, then removed by valve 23 and line 29. A cross-flow stream of air across the silica liquid stream is provided by line 30.

The process operates as follows: Fresh stable aqueous sodium silicate solution is introduced through line 31 whereupon it passes to atomizing nozzle II by line In and pump 24. The stream, composed of microspheres of various sizes, is projected at an oblique angle I2 into an inert gaseous atmosphere I3, advantageously air. The droplets assume different trajectors -3I, 32, 33

and 34 depending upon air friction, gravity and the mass velocity force. By the proper positioning of barriers I7, i8 and I9 only those droplets of desired size are passed to the acidic environment, as illustrated by trajectory 32. A crossilow gas stream from line located at an intermediate point between the discharge orifice I I and the collecting means will vary the paths of ti e droplets so that the undesired droplets will not pass into the acidic gelling zone I4. That is, since the silica droplets may emerge from the nozzle at different velocities, this cross-flow stir will provide means so that droplets of low velocity-high mass and high velocity-low mass will not follow identical trajectories and thus impair somewhat the accuracy of the size classification. vertically inclined so that the silicate droplets of undesired size are collected as a solution, and then passes by lines 20, 2| and 221, to line 23 for recycling to the discharge nozzle. Troughs ll and is are placed so that there is an opening between them, allowing passage of droplets in the trajectory 32. The troughs on their overlapping ends 35 and 35 are finished so that the particles cannot splatter or otherwise-deform While pass ing into the acid environment. The upper acid layer I5 comprises sulfur dioxide dissolved in oil; the gaseous S02 may thus rise to the collection troughs and gel the solutions therein prior to recycling; to prevent this a vent 25 is provided through which this S02 is drawn on by pump 25. The silicate droplets pass through the acid layers and are gelled. The microspheres of silica hydrogel thus formed and size classified are collected at the bottom 21 of the acid zone It and removed by line 29 through valve 23.

I claim:

1'. The method of forming and size classifying small, substantially spherical, solid particles which comprises discharging a body of aqueous sodium silicate solution as a stream of droplets at an oblique angle, segregating the discharged liquid droplets into at least two fractions ac-- cording to the difference of their trajectories, collecting one of said fractions while still liquid, recycling said fraction to said body of aqueous sodium silicate solution, solidifying another fraction of said droplets by contacting with a fluid acidic medium, and collecting the solidified fraction.

2. The method of claim 1 wherein the discharged stream of droplets is subjected to a cross-flow gas stream to improve size classification of the droplets according to their assumed trajectories by further modifying the paths of the droplets according to size.

JOHN L. GRING.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 518,082 Stuckey Apr. 10, 1894 881,296 Briddon et al Jan. 10, 1907 1,358,375 Koch Nov. 9, 1920 1,660,682 Stebbins Feb. 28, 1928 1,843,576 McClure Sept. 2:, 1932 2,255,206 Duncan Sept. 9, 1941 2,338,779 Mutch Jan. 11, 1944 2,435,158 Read Jan. 27', 1948 2,506,316 Pierce May 2, 1950 The collection troughs ll, I8 and H] are 

1. THE METHOD OF FORMING AND SIZE CLASSIFYING SMALL, SUBSTANTIALLY SPHERICAL, SOLID PARTICLES WHICH COMPRISES DISCHARGING A BODY OF AQUEOUS SODIUM SILICATE SOLUTION AS A STREAM OF DROPLETS AT AN OBLIQUE ANGLE, SEGREGATING THE DISCHARGED LIQUID DROPLETS INTO AT LEAST TWO FRACTIONS ACCORDING TO THE DIFFERENCE OF THEIR TRAJECTORIES, COLLECTING ONE OF SAID FRACTIONS WHILE STILL LIQUID, RECYCLING SAID FRACTION TO SAID BODY OF AQUEOUS SODIUM SILICATE SOLUTION, SOLIDIFYING ANOTHER 